WO2019103457A1 - Rubber composition - Google Patents

Abstract

The present invention relates to a rubber composition comprising a conjugated diene polymer and having excellent tensile characteristics and viscoelastic characteristics. The rubber composition according to the present invention can selectively comprise a modified conjugated diene polymer suitable for desired tensile characteristics and viscoelastic characteristics, by in advance predicting the correlation between a modification rate of the modified conjugated diene polymer and a dynamic viscoelastic loss coefficient at 60°C of the rubber composition through mathematical expressions (1) and (2), and thus the rubber composition can exhibit excellent combination characteristics.

Description

Rubber composition

Mutual citation with related application

This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0155606, filed on November 21, 2017, the entire contents of which are incorporated herein by reference.

Technical field

The present invention relates to a rubber composition comprising a conjugated diene polymer having excellent tensile properties and viscoelastic properties.

Recently, interest in energy conservation and environmental issues has increased, and fuel economy of automobiles has been demanded. As one of the methods for achieving this, a polymer having a rolling resistance less than that of a rubber material for a tire, excellent in abrasion resistance and tensile properties, and having stability stability represented by wet skid resistance is required.

In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As the evaluation index of such vulcanized rubber, rebound resilience of 50 to 80 캜, tan δ and Goodrich heating are used. A rubber material having a large rebound resilience or a small tan δ or good rich heat generation is preferable.

Natural rubbers, polyisoprene rubbers, polybutadiene rubbers, and the like are known as rubber materials having a small hysteresis loss, but these have a problem of low wet skid resistance. Recently, a conjugated diene polymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) is prepared by emulsion polymerization or solution polymerization and is used as a rubber for a tire. Of these, the greatest advantage of solution polymerization over emulsion polymerization is that vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled and molecular weight and physical properties, etc., can be controlled by coupling, It can be adjusted. Therefore, it is possible to easily change the structure of the finally prepared SBR or BR rubber, to reduce the movement of chain ends due to bonding or modification of chain ends, and to increase the bonding force with a filler such as silica or carbon black, Is widely used as a rubber material for a tire.

On the other hand, when the conjugated diene polymer is modified, the modified region greatly influences compounding processability and physical properties through interaction with an inorganic filler at the time of preparing a rubber composition, and this is because the modification ratio of the conjugated diene polymer, Is determined depending on how much the polymerization active site of the diene polymer is modified. Accordingly, the modification ratio is utilized as an important index in determining the physical properties of the rubber composition.

In this regard, Japanese Patent Publication No. 5698560 discloses a relative measurement method using polystyrene gel using Gel Permeation Chromatography (GPC) as a method of measuring the above-described modification ratio. Specifically, a standard polystyrene which does not adsorb to a column is added to a sample by using a silica-based column capable of adsorbing denatured components and a polystyrenic column not adsorbing denatured components, respectively, to measure the refractive index (The hatched area in FIG. 1) of the refracting index (RI), the transformation rate is calculated according to the following equation (3).

&Quot; (3) "

However, since the metamorphic rate measurement by gel permeation chromatography requires a separate reference material called polystyrene and the conversion rate is calculated from the comparison of the chromatogram to the reference material and the mixture of the reference material and the polymer, There is a problem that accuracy is not guaranteed.

[Prior Art Literature]

[Patent Literature]

(Patent Document 1) JP5698560 B

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art, and it is an object of the present invention to provide a rubber composition comprising a conjugated diene polymer having excellent tensile properties and viscoelastic properties.

According to one embodiment of the present invention for solving the above problems, the present invention provides a modified conjugated diene polymer; Filler; And a vulcanizing agent, and satisfies the following formula (1): < EMI ID = 1.0 >

[Equation 1]

In the above formula (1), X is the modifying rate of the modified conjugated diene polymer,

A is a dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of a rubber composition containing an unmodified conjugated diene polymer and has a real value of 0.147 to 0.160,

Y is the dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of the rubber composition containing the modified conjugated diene polymer.

The rubber composition according to the present invention contains a modified conjugated diene polymer and can control the purity of a modifier satisfying the formula (1) to include a modified conjugated diene polymer having a high modifying ratio, thereby exhibiting excellent tensile properties and viscoelastic properties have.

Further, the rubber composition of the present invention can predict the correlation between the modifying ratio of the modified conjugated diene polymer and the dynamic viscoelastic loss coefficient of the rubber composition at 60 DEG C in advance in accordance with Equation (1) so as to satisfy the desired tensile and viscoelastic properties It is possible to selectively use a modified conjugated diene polymer. By controlling the modifying ratio through the purity of the modifying agent and providing a rubber composition having an excellent viscoelasticity coefficient under the controlled modifying rate, a rubber composition having excellent viscoelastic properties can be obtained It is possible to have a high reproducibility in providing.

1 is a graph showing a correlation between a dynamic viscoelastic loss coefficient at 60 ° C and a modifying ratio of a modified conjugated diene polymer according to an embodiment of the present invention.

FIG. 2 is a chromatogram showing the change in detection solution according to the second solvent injection in the metamorphic rate measuring method according to an embodiment of the present invention. FIG.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the description of the present invention and in the claims should not be construed to be limited to ordinary or dictionary terms and the inventor should appropriately interpret the concept of the term appropriately The present invention should be construed in accordance with the meaning and concept consistent with the technical idea of the present invention.

As used herein, the term " substituted " means that the hydrogen of a functional group, an atomic group or a compound is substituted with a specific substituent, and when a hydrogen atom of a functional group, an atomic group or a compound is substituted with a specific substituent, One or more than two substituents may be present depending on the number of hydrogen atoms. When a plurality of substituents are present, the respective substituents may be the same as or different from each other.

The term " alkyl group " used in the present invention may mean a monovalent aliphatic saturated hydrocarbon and includes linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl, , Tert-butyl, and neo-pentyl. The term " alkyl "

In the present invention, the "cycloalkyl group" may mean a cyclic saturated hydrocarbon or a cyclic unsaturated hydrocarbon containing one or more unsaturated bonds.

The term " aryl group " used in the present invention means a cyclic aromatic hydrocarbon, and may be a monocyclic aromatic hydrocarbon having one ring formed therein or a polycyclic aromatic hydrocarbon having two or more rings bonded thereto polycyclic aromatic hydrocarbons.

The present invention provides a rubber composition comprising a conjugated diene polymer having excellent tensile properties and viscoelastic properties.

The rubber composition according to one embodiment of the present invention is a modified conjugated diene polymer modified with a modifier having a purity of 92.0% or more; Filler; And a vulcanizing agent, and is characterized by satisfying the following formula (1).

[Equation 1]

Wherein A is the dynamic viscoelastic loss coefficient (tan delta) of the rubber composition containing the unmodified conjugated diene polymer at 60 DEG C, Y is the modulus of the modified conjugated diene polymer Is the dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of the rubber composition containing the diene polymer.

In the above, A may specifically have a value of 0.140 to 0.160, and Y may specifically be 0.05 or more and 0.14 or less.

Wherein A is the dynamic viscoelastic loss coefficient of the unmodified conjugated diene polymer, which may have somewhat different values, depending on the polymer product marketed, and depending on the conditions of the measurement, and is generally between 0.140 and 0.160 Usually 0.147 to 0.160, and may have a value of 0.150 or more.

The rubber composition according to one embodiment of the present invention is characterized in that the modulus of the modified conjugated diene polymer and the dynamic viscoelastic loss coefficient at 60 캜 of the rubber composition containing the unmodified polymer are used to determine the dynamic And the viscoelastic loss coefficient of the modified conjugated diene polymer may be predicted through the formula 1 to select the modified conjugated diene polymer containing the modified conjugated diene polymer and having the modified ratio adjusted to the desired tensile and viscoelastic properties So that it is easy to have excellent tensile properties and viscoelastic properties.

That is, if only the information on the dynamic viscoelastic loss coefficient of the unmodified unmodified conjugated diene polymer is known, the dynamic viscoelastic loss coefficient of the modified conjugated diene polymer can be predicted according to the degree of modification, It is possible to predict the compounding properties even if the polymer alone is not used.

The modified conjugated diene polymer is characterized in that the modifier has a purity of at least 90.0%. The purity of the modifier is a factor affecting the modifying rate. When the modifying agent has a purity of 90.0% or more, an excellent modifying rate is achieved .

In the past, the importance of the purity of the denaturant has not been recognized, and the losses such as cost and time for purification have been considerable in order to utilize those having high purity. However, in the present invention, it is discovered that the purity of the modifier is a factor related to the modifier, and the modifier is controlled at an appropriate level to provide a modified conjugated diene polymer having an excellent modifier.

The appropriate level of purity should be at least 90.0%, preferably at least 92.0%, more preferably at least 93.0%. In addition, when the purity of the modifier is higher than 90%, the modifying rate may increase greatly, and when the purity of the modifying agent is higher than 93%, it may increase again.

Further, the above formula (1) can predict the correlation between the modification ratio of the modified conjugated diene polymer and the dynamic viscoelastic loss coefficient at 60 캜 of the rubber composition, and it is possible to predict the properties required in the production of the modified conjugated diene polymer It is possible to predict in advance whether the modifying rate of the polymer should be adjusted to a certain level and which can be predicted through the purity of the modifier. Therefore, in the production of the modified conjugated diene polymer, selection of the modifier, target modifying rate selection, It is possible to provide information that is effective for selection, and further, it is possible to provide a rubber composition having excellent viscoelastic properties with high reproducibility.

In the present invention, 11 modified conjugated diene-based polymers having different modifying ratios are prepared, and the dynamic viscoelastic loss coefficient at 60 ° C is measured using the rubber composition containing the modified conjugated diene polymer, A graph of a comparison between the polymer and the dynamic viscoelastic loss coefficient is prepared, and the result is a regression equation (see FIG. 1).

In the present invention, the Y value represents the range of the dynamic viscoelastic loss coefficient of the rubber composition at 60 DEG C as described above. When the above-mentioned range is satisfied, the Y value shows a balance in both tensile and viscoelastic properties can do.

In one embodiment of the present invention, the modified conjugated diene polymer includes a lanthanide-based rare earth element-containing catalyzed conjugated diene polymer having at least one terminal functional group, specifically, a functional group having at least one terminal and / Modified polymer comprising a modified polymer unit containing a functional group and an unmodified polymer unit containing no functional group. That is, in the present invention, the modified polymer unit and the unmodified polymer unit represent a constituent unit constituting one polymer, and the conjugated diene polymer may be composed of a denatured polymer unit and an unmodified polymer unit. Here, the functional group may be a functional group derived from a modifier such as a filler-affinity group.

In one embodiment of the present invention, the method for producing a modified conjugated diene-based polymer comprises polymerizing a conjugated diene-based monomer in the presence of a lanthanum-based rare earth element catalyst composition to prepare an active polymer containing an organic metal moiety A); And a denaturing reaction step of reacting the denaturant with the active polymer.

Here, the active polymer preparation step and the denaturation step can be generally carried out in accordance with the reaction conditions applicable in the art, and can be carried out, for example, by solution reaction or solid phase reaction, have. As another example, the polymerization and the modification reaction of the active polymer may be carried out using a batch reactor, or may be carried out continuously using an apparatus such as a multi-stage continuous reactor or an inline mixer.

As another example, the polymerization reaction and the modification reaction can usually be carried out under similar temperature and pressure conditions, and can be carried out, for example, at a temperature of from 20 to 100 ° C, within which the viscosity of the polymer does not rise, The activated end of the membrane is not inactivated.

The lanthanide-based rare earth element-catalyzed conjugated diene-based polymer may be a conjugated diene-based polymer derived from a catalyst composition comprising a lanthanide rare earth element-containing compound, that is, an activated organometallic site derived from a catalyst, And may be prepared by polymerizing the conjugated diene monomer in the presence of the catalyst composition. Here, the conjugated diene-based polymer may be a butadiene homopolymer such as polybutadiene, or a butadiene copolymer such as a butadiene-isoprene copolymer.

Specifically, the conjugated diene-based polymer contains 80 to 100% by weight of repeating units derived from 1,3-butadiene monomer and 20% by weight or less of other conjugated diene monomer-derived repeating units copolymerizable with 1,3-butadiene And the 1,4-cis bond content in the polymer is not lowered within the above range. Examples of the 1,3-butadiene monomer include 1,3-butadiene, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, And other conjugated diene monomers copolymerizable with 1,3-butadiene may include 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene , 4-methyl-1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene, and any one or two or more of them may be used.

According to an embodiment of the present invention, the conjugated diene-based polymer may be a neodymium-catalyzed butadiene-based polymer containing repeating units derived from 1,3-butadiene monomers.

In the present invention, the activated organometal moiety of the conjugated diene polymer means an activated organometal moiety at the terminal of the conjugated diene polymer (an activated organometal moiety at the molecular chain terminal), an activated organometallic moiety in the main chain or a side chain , And among these, when an activated organometallic moiety of the conjugated diene polymer is obtained by anionic polymerization or coordination anionic polymerization, the activated organometallic moiety may be a terminal activated organic metal moiety .

On the other hand, the catalyst composition may contain a lanthanide-based rare earth element-containing compound, an alkylating agent, and a halogen compound.

The lanthanide-based rare-earth element-containing compound can be used without any particular limitation as long as it is ordinarily used in the production of the conjugated diene-based polymer. For example, the lanthanide-based rare earth element-containing compound may be an organometallic compound having an atomic number such as lanthanum, neodymium, cerium, gadolinium or praseodymium Any one or two or more of the rare earth metals of 57 to 71 may be a compound, and more specifically may be a compound containing any one or two or more selected from the group consisting of neodymium, lanthanum and gadolinium.

The lanthanide-based rare earth element-containing compound may be at least one selected from the group consisting of the rare earth metal-containing carboxylate (for example, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, (For example, neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, and the like) , Neodymium dioctylphosphate, neodymium dioctylphosphate, neodymium bis (1-methylheptyl) phosphate, neodymium bis (2-ethylhexyl) phosphate or neodymdidecylphosphate), organic phosphonates Pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, Neodymium dodecylphosphonate, neodymium dodecylphosphonate or neodymium octadecylphosphonate, and the like), a metal salt such as neodymium octylphosphonate, neodymium (1-methylheptyl) phosphonate, neodymium (2-ethylhexyl) Organic phosphoric acid salts such as neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl) phosphinate or Neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, or neodymium (2-ethylhexyl) phosphite) Dibenzylcarbamate, and the like), dithiocarbamates (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium di (For example, neodymium methyl xanthate, neodymium ethyl xanthate, neodymium isopropyl xanthenate, neodymium dibutyl dithiocarbamate, etc.), xanthate (For example, neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoyl acetoacetate, or neodymium benzoyl acetoacetate) (Neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonylphenoxide, etc.), halides or pseudohalides (neodymium fluoride, neodymium bromide, etc.), alkoxides or allyl oxides Neodymium chloride, neodymium bromide, neodymium iodide, neodymium (Such as neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide), or at least one rare earth metal-carbon bond (such as cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide) (E.g., Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn (cyclooctatetraene), (C ₅ Me ₅ ) ₂ LnR, LnR ₃ , Ln (allyl) _3, or Ln (allyl) ₂ Cl, etc., wherein wherein Ln is a rare earth metal element, R is a hydrocarbyl group as defined above) and the like, any one or a mixture of two or more of these .

Specifically, the lanthanide rare earth element-containing compound is at least one compound selected from the group consisting of Nd (2,2-diethyldecanoate) ₃ , Nd (2,2-dipropyldecanoate) ₃ , Nd (2,2-dibutyldecanoate) _3, Nd (2,2- di-hexyl decanoate) _3, Nd (2,2- dioctyl decanoate) _3, Nd (2- ethyl-2-propyl decanoate) _3, Nd (2- ethyl 2-butyl decanoate) _3, Nd (2- ethyl-2-hexyl decanoate) _3, Nd (2- butyl-2-propyl decanoate) _3, Nd (2- propyl-2-hexyl de decanoate) _3, Nd (2- propyl-2-isopropyl decanoate) _3, Nd (2- butyl-2-hexyl decanoate) _3, Nd (2- cyclohexyl-2-octyl decanoate) ₃ , Nd (2,2- diethyl octanoate) _3, Nd (2,2- dipropyl octanoate) _3, Nd (2,2- dibutyltin octanoate) _3, Nd (2,2- di hexyl octanoate) _3, Nd (2- ethyl-2-propyl-octanoate) _3, Nd (2- ethyl-hexyl-2-octanoate) _3, Nd (titeu to 2,2-diethyl-no nano) _3, Nd (2,2- dipropyl no nano this ) _3, Nd (2,2- dibutyl no nano-benzoate) _3, Nd (2,2- dihexyl no nano-benzoate) _3, Nd (2- Ethyl-2-propyl-no nano-benzoate) ₃ and Nd (2- Ethyl-2-hexyl nonanoate) ₃ , or a mixture of two or more thereof. Considering the excellent solubility in a polymerization solvent, the conversion to a catalytically active species, and the effect of improving catalytic activity thereby, without concern for oligomerization, the neodymium compound is preferably Nd (2,2-diethyl decanoate) _3, Nd (2,2- dipropyl decanoate) _3, Nd (2,2- di-butyl decanoate) _3, Nd (2,2- di-hexyl decanoate) _3, and Nd (2,2 -Dioctyl decanoate) ₃ , or a mixture of two or more thereof.

The alkylating agent may be an organic metal compound or a boron-containing compound which is soluble in a non-polar solvent, specifically, a non-polar hydrocarbon solvent, and contains a cationic metal such as a Group 1, Group 2 or Group 3 metal and a carbon. More specifically, the alkylating agent may be any one or a mixture of two or more selected from the group consisting of an organoaluminum compound, an organomagnesium compound, and an organolithium compound.

The organoaluminum compound may be selected from the group consisting of diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH) N-propyl aluminum hydride, phenyl isopropyl aluminum hydride, phenyl isopropyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, n-butyl aluminum hydride, phenyl isobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, , p-tolyl-n-butyl aluminum hydride, p-tolyloisobutyl aluminum hydride N-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride, benzyl isobutyl aluminum hydride, Or dihydrocarbylaluminum hydride such as benzyl-n-octylaluminum hydride; Hydrocarbylaluminum such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride or n-octylaluminum dihydride, Dihydride and the like. In addition, the organoaluminum compound may be aluminoxane. The aluminoxane can be prepared by reacting a trihydrocarbyl aluminum compound with water. More specifically, the aluminoxane may be at least one selected from the group consisting of methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, Aluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane or 2,6-dimethylphenyl Aluminoxane, and the like, and any one or a mixture of two or more of them may be used.

The organomagnesium compound includes at least one magnesium-carbon bond, and is a non-polar solvent, specifically, a magnesium compound soluble in a non-polar hydrocarbon solvent. Specifically, the organomagnesium compound may be an alkylmagnesium compound such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, or dibenzylmagnesium; Hydrocarbyl magnesium hydrides such as methylmagnesium hydride, ethylmagnesium hydride, butylmagnesium hydride, hexylmagnesium hydride, phenylmagnesium hydride and benzylmagnesium hydride; There may be mentioned methylmagnesium chloride, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, butylmagnesium bromide, hexylmagnesium bromide, phenylmagnesium bromide, Hydrocarbyl magnesium halides such as magnesium bromide and the like; Hydrocarbyl magnesium carboxylates such as methyl magnesium hexanoate, ethyl magnesium hexanoate, butyl magnesium hexanoate, hexyl magnesium hexanoate, phenyl magnesium hexanoate and benzyl magnesium hexanoate; Hydrocarbyl magnesium alkoxides such as methyl magnesium ethoxide, ethyl magnesium ethoxide, butyl magnesium ethoxide, hexyl magnesium ethoxide, phenyl magnesium ethoxide and benzyl magnesium ethoxide; Or hydrocarbyl magnesium aryloxides such as methyl magnesium phenoxide, ethyl magnesium phenoxide, butyl magnesium phenoxide, hexyl magnesium phenoxide, phenyl magnesium phenoxide, benzyl magnesium phenoxide and the like.

As the organic lithium compound as the alkylating agent, alkyl lithium of R-Li (wherein R is an alkyl group having 1 to 20 carbon atoms, more specifically a linear alkyl group having 1 to 8 carbon atoms) may be used. More specifically, there may be mentioned methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, isobutyllithium, pentyllithium, isopentyllithium, Two or more mixtures may be used.

Examples of the halogen compound include a halogen compound, an interhalogen compound, a hydrogen halide, an organic halide, a nonmetal halide, a metal halide or an organic metal halide, and any one or a mixture of two or more thereof Can be used. Among them, one or a mixture of two or more selected from the group consisting of an organic halide, a metal halide, and an organometallic halide may be used as the halogen compound, considering that the catalytic activity is improved and the reactivity is improved.

Specifically, examples of the halogen group include fluorine, chlorine, bromine, and iodine.

Specific examples of the halogen compound include iodine monochloride, iodine monobromide, iodine trichloride, iodopentafluoride, iodine monofluoride and iodotrifluoride.

Examples of the hydrogen halide include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.

Specific examples of the organic halide include t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chlorodi-phenyl methane, bromo- , Triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide , Propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also referred to as iodoform), tetraiodomethane, 1 - iodopropane, 2-iodopropane, 1,3-diiodopropane, t-butyliodide, 2,2-dimethyl-1-iodopropane (Also referred to as " pentyl iodide "), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide Triethylsilyl iodide, trimethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyl Triiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide or methyl iodoformate, and the like.

Further, as the non-metal halides specifically include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, oxy-bromide, phosphorus, boron trifluoride, boron trichloride, boron tribromide, used silicon tetrafluoride, silicon tetrachloride (SiCl _4), four There may be mentioned silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, silicon carbide, Selenium and the like.

Specific examples of the metal halide include tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony trichloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, A metal oxide such as indium, tin bromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc bromide, zinc fluoride, aluminum triiodide, gallium triiodide, indium triiodide, titaniumiodide, zinc iodide, Germanium tetraiodide, tungsten iodide, antimony triiodide, or magnesium iodide.

Specific examples of the organometallic halide include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methyl (EASC), isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, ethylmagnesium bromide, ethylmagnesium bromide, ethylmagnesium bromide, , Ethylmagnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium Butyl tin dichloride, di-t-butyl tin dibromide, di-n-butyl tin dichloride, di-n-butyl tin dichloride, n-butyltin chloride, tri-n-butyltinbromide, methylmagnesium iodide, dimethyl aluminum iodide, diethyl aluminum iodide, di-n-butyl aluminum iodide Diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, methyl aluminum sesiodide Quaternary ammonium salts such as quaternary ammonium salts, quaternary ammonium salts, quaternary ammonium salts, quaternary ammonium salts, quaternary ammonium salts, quaternary ammonium salts, quaternary ammonium salts, N-butyl iodide, tri-n-butyl tin iodide, di-n-butyl iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, Tin diiodide or di-t-butyltin diiodide, and the like.

The catalyst composition according to an embodiment of the present invention may further include a diene monomer in addition to the above components.

The diene-based monomer may be mixed with a polymerization catalyst to form a premixing catalyst, or may be prepared by polymerization with components in a polymerization catalyst, specifically an alkylating agent such as DIBAH, to form a preforming catalyst . When the prepolymerization is performed in this manner, the activity of the catalyst can be improved, and the conjugated diene-based polymer to be produced can be further stabilized.

Specifically, the diene-based monomer can be used without particular limitation, as long as it is usually used in the production of a conjugated diene-based polymer. Specifically, the diene monomer may be at least one monomer selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, Methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene. Of these, One or a mixture of two or more may be used.

The catalyst composition according to an embodiment of the present invention may further include a hydrocarbon-based solvent in addition to the above-mentioned components.

The hydrocarbon-based solvent may specifically be a nonpolar solvent which is not reactive with the above-mentioned catalyst components. Specific examples include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclopentane, , Methylcyclopentane or methylcyclohexane, and the like; alicyclic hydrocarbons having 5 to 20 carbon atoms in a linear, branched, or cyclic form; A mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms such as petroleum ether or petroleum spirits, or kerosene; Or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, etc., and any one or a mixture of two or more of them may be used. More specifically, the non-polar solvent may be any of the above-described linear, branched or cyclic aliphatic hydrocarbons or aliphatic hydrocarbons of 5 to 20 carbon atoms, more specifically, n-hexane, cyclohexane, .

The modifier may be selected from those conventionally known in the art depending on the polymer and the purpose of modification, and examples thereof include azacyclo propane, ketone, carboxyl, thiocarboxyl, carbonate, carboxylic anhydride, (Wherein M is selected from Sn, Si, Ge and P, and is selected from the group consisting of a halogen atom, a cyano group, a thiourea group, an amide group, a thioamide group, an isocyanate group, a thioisocyanate group, a halogenated isocyano group, an epoxy group, a thioepoxy group, And Z is a halogen atom), and does not contain an active proton and an onium salt. Accordingly, the action path can be variously selected accordingly.

As another example, the modifier may be a compound represented by the following formula (1) or (2).

[Chemical Formula 1]

(2)

In the above formula (1) or (2)

Z ₁ and Z ₂ are each independently a silane group, an N, N-2 substituted aminophenyl group, an imine group or a cyclic amino group, R ₁ and R ₇ are independently a single bond or a divalent organic group,

R ₃ and R ₆ are, independently of each other, a single bond or a divalent organic group; Each of which is a trivalent organic group connected to R ₄ or R ₅ and R ₈ or R ₉ to form a ring, R ₄ and R ₈ are each independently a monovalent organic group; Or a divalent organic group each of which is linked to R ₃ or R ₅ and R ₆ or R ₉ to form a ring, and R 5 is a monovalent organic group; Or R < ₃ > or R < ₄ > to form a ring.

Specifically, the modifier represented by Formula 1 or Formula 2 is, for example, N- (3-triethoxysilylpropyl) -4,5-dihydroimidazole, N- (1,3-dimethylbutylidene) -Triethoxysilyl) -1-propanamine, oligomers of these, or mixtures thereof; dimethylaminobenzylideneethylamine, diethylaminobenzylidenebutylamine dimethylaminobenzylidene aniline, dimethylaminobenzylidene n-butyl aniline, dimethyl (Dimethylaminophenyl) methylidenebutylamine, bis (dimethylaminophenyl) methylidene n-octylamine, bis (diethylaminobenzylidene) methoxyaniline, (Ethylaminophenyl) methylidenebutylamine, bis (diethylaminophenyl) methylidene n-octylamine, benzylidene dimethylaminoaniline, methoxybenzylidene dimethylaminoaniline, 1-methyl- Alkylidene-dimethylaniline, 1,3-dimethyl-butylidene-dimethylaniline, or mixtures thereof; Phenylenebis (dimethylaminobenzylideneamine); Aniline such as benzylidene (1-hexamethyleneimino) aniline, benzylidene (1-pyrrolidino) aniline, dimethylaminobenzylidene (1-hexamethyleneimino) aniline, dimethylaminobenzylidene (1-pyrrolidino) Benzylidene aniline, benzylidene aniline, benzylidene ((4-n-butyl-1-piperazino) methyl) aniline, benzylidene ((3- ( Methyl) pyrrolidino) methyl) aniline, ((4-n-butyl-1-piperazino) methyl) benzylidene aniline, Or a mixture thereof.

In one embodiment of the present invention, the modification ratio is a value calculated according to the following formula (2) using a chromatogram obtained from a chromatographic measurement, and the chromatography measurement includes a modified polymer unit and an unmodified polymer unit Preparing a first solution by dissolving the polymer in a first solvent; Injecting the first solution into a column filled with adsorbent; Adsorbing the modified polymer unit to the adsorbent, and eluting the first solution in which the unmodified polymer unit is dissolved; Transferring the eluted first solution to a detector; Introducing a second solvent into the column to elute the second solution in which the adsorbed modified polymer units are dissolved; And transferring the eluted second solution to the detector.

&Quot; (2) "

Wherein the peak area of the unmodified polymer unit is the peak area of the chromatogram for the first solution transferred to the detector and the peak area of the modified polymer unit is for the second solution transferred to the detector The peak area of the chromatogram.

In the present invention, the modifying ratio may mean, for example, a ratio of a modified polymer to an unmodified polymer when the polymer is modified with a modifier for a polymer having a polymerizable active site in the polymer, Can be expressed as percentage (%) with respect to the whole polymer and the unmodified polymer.

In the present invention, the column may be a column that can be used for chromatography, for example, a normal phase column in which the stationary phase is polar and the mobile phase is non-polar, or The stationary phase may be a reverse phase column, which is nonpolar and the mobile phase is polar.

The adsorbent according to an embodiment of the present invention means a stationary phase of the column. The adsorbent according to an embodiment of the present invention may be a filler to be packed in the column, and may be appropriately selected depending on the denaturation site modified by the denaturant. The adsorbent may be one selected from the group consisting of a silica-based adsorbent, a polymer-based adsorbent, an alumina (Al ₂ O ₃ ) adsorbent, a graphitized carbon adsorbent and a zirconia adsorbent, Adsorption of various modified polymers can be facilitated.

The silica-based adsorbent may be, for example, a silica gel adsorbent derived from silica (SiO ₂ ); And a silanol (Si-OH) group on the silica gel surface is selected from the group consisting of a chain, branched or cyclic alkylsilane having 1 to 30 carbon atoms, arylsilane having 5 to 30 carbon atoms, a chain, branched or cyclic alkylsilyl An adsorbent which is substituted or end-capped with at least one group selected from the group consisting of an anisilane and a chain, branched or cyclic aminoalkylsilane having 1 to 30 carbon atoms, and an adsorbent selected from the group consisting of Specific examples thereof include a silica gel adsorbent; (Dimethyl) silane, octadecyl (dimethyl) silane, cyanopropyl (dimethyl) silane, amino (ethyl) silane, ethyl (dimethyl) silane, propyl (dimethyl) silane, butyl Capped with an at least one derived group selected from the group consisting of propyl (dimethyl) silane and 4-phenylbutyl (dimethyl) silane.

The adsorbent may have a particle size of 0.001 to 100 mu m, 1 to 100 mu m, 1 to 50 mu m, or 3 to 30 mu m, for example. Within this range, adsorption of the modified polymer is easy. The size of the particles may mean an average particle diameter depending on the type of the adsorbent. For example, when the adsorbent is spherical or ellipsoidal, it may mean an average particle diameter or a long axis. In the case of a polyhedron, it may mean an average particle diameter with respect to a long axis.

Meanwhile, in the method for measuring the modifying rate of the conjugated diene polymer according to an embodiment of the present invention, different adsorbents can be applied depending on the modified polymer, and specifically, the modified polymer according to one embodiment of the present invention has at least one terminal , And the adsorbent may be a silica-based adsorbent substituted with a functional group containing an amine group.

According to an embodiment of the present invention, the first solvent and the second solvent may be independently polar solvent or nonpolar solvent, and more specifically, when the first solvent is polar solvent, the second solvent is non- And when the first solvent is nonpolar solvent, the second solvent can be polar solvent, and in this case, the effect of eluting the unmodified polymer from the first solution and the modified polymer from the second solution more efficiently, respectively have.

As another example, the first solvent and the second solvent may be each independently polarity dielectrics having different polarities, and specifically, when the first solvent is a polarity solvent having a high polarity, Wherein the second solvent can be a polarity solvent having a high polarity, and the polarity is not an absolute value, and the first solvent can be a polar solvent having a low degree of polarity, May be a relative concept depending on the polarity of the polar solvent used for the solvent and the second solvent, respectively. In this case, there is an effect of eluting the unmodified polymer from the first solution and the modified polymer from the second solution more efficiently.

The polar solvent may be used in chromatography and is not particularly limited as long as it is a polar solvent capable of dissolving the modified polymer and the unmodified polymer. Examples of the polar solvent include water, methanol, ethanol, n-propanol, n-butanol, isopropanol, (DMF) such as acetic acid, acetone, nitromethane, propylene carbonate, 1,2-dioxane, 1,3-dioxane, 1,4-dioxane, tetrahydrofuran (THF), acetonitrile (MeCN) , Dimethyl sulfoxide (DMSO), methyl ethyl ketone, benzonitrile, pyridine, nitroethane, benzyl alchol, methoxy ethanol, and formamide. Or more.

The nonpolar solvent may be used in chromatography and is not particularly limited as long as it is a polar solvent capable of dissolving the modified polymer and the unmodified polymer. Examples thereof include hexane, benzene, toluene, diethylether, chloroform, ethyl acetate, dichloromethane, It may be at least one selected from the group consisting of cyclohexane, tetrachloromethane, iso-octane, xylene, butyl ether, isopropyl ether and ethylene chloride.

According to an embodiment of the present invention, the first solvent can be injected at a flow rate of 0.01 to 10.0 ml / min, or 0.5 to 2.0 ml / min, and more efficiently within this range adsorbs the modified polymer to the adsorbent And only the unmodified polymer is eluted together with the first solution.

According to one embodiment of the present invention, the second solvent can be injected at a flow rate of 0.01 to 10.0 ml / min, or 0.5 to 2.0 ml / min, and the modified polymer adsorbed to the adsorbent more efficiently within this range There is an effect of eluting the dissolved second solution.

In addition, the first solution and the second solution may be adjusted so as to facilitate elution of the unmodified polymer or the second solution within the above-described range depending on the column capacity (column length or diameter), respectively.

According to one embodiment of the present invention, the second solvent may be injected after the entire amount of the unmodified polymer is eluted. The time point at which the entire amount of the unmodified polymer is eluted may mean the point at which the signal of the unmodified polymer is no longer detected from the detector. As another example, the second solvent may be injected into the column into which the first solution is injected after the completion of the injection of the first solution, and specifically, the first solvent may be injected into the first solution injected column by gradient elution, The solution can be continuously injected into the injected column. In this case, there is an effect that more accurate measurement can be performed without interruption of the signal at the time of detection.

According to one embodiment of the present invention, when the second solvent is continuously injected into the column into which the first solution is injected according to the gradient elution method, the first solution and the second solution are injected from the time when the second solvent is injected The simultaneously eluted first and second solutions can be simultaneously delivered to the detector. In addition, the content of the first solution and the second solution from the injection time point of the second solvent is 100% by volume based on the content of the first solution and the second solution transferred to the detector, 1 solution may be gradually increased or decreased from 100% by volume to 0% by volume and the second solution may be gradually increased or decreased from 0% by volume to 100% by volume. As a specific example, the first solution and the second solution can be detected simultaneously in the detector from the injection point of the second solvent, and the detection amount of the first solution injected in accordance with the injection of the second solvent is 100 volume% to 0 volume% The detection amount of the second solution increases from 0 vol% to 100 vol% as the detection amount of the first solution decreases, and only when the elution of the first solution is completed, only the second solution may be detected 2).

According to one embodiment of the present invention, the conjugated diene-based polymer modification ratio is measured by using a chromatographic measuring instrument. For example, a liquid chromatographic measuring instrument can be used. As a specific example, A mobile phase reservoir for storing the solvent, a pump for supplying a constant and reproducible moving phase to the column, a sample injector for adjusting the injection volume of the solution or solvent injected into the column, a modified polymer and unmodified A column for separating the polymer and a chromatographic measuring instrument comprising an eluted denatured polymer or a detector for sensing the unmodified polymer.

The moving-phase storage device may include two or more mobile phase storage devices. For example, a mobile phase storage device for storing the first solution and a mobile phase storage device for storing the second solvent may be separately provided. In addition, the mobile phase reservoir may include a separate gradient elution device for application of gradient elution.

The pump generates a pressure of, for example, 0.1 to 10,000 psi or 100 to 5,000 psi, adjusts the flow rate of 0.01 to 20 ml or 0.1 to 10 ml, has no pulse during solution or solvent supply, The rate of change may be maintained at 1% or less, or 0.1 to 0.5%. In another example, the pump may be a single-head pump or a dual-head pump, and may be a dual-head pump, in which case a gradient elution) can be easily applied.

The injector may be, for example, a Rheodyne injector or an automatic injector. The injector may include, for example, a loop having a volume of 1 to 500 μl, 5 to 200 μl, 100 < / RTI > < RTI ID = 0.0 > pL. ≪ / RTI >

The detector may be, for example, selected from a UV / Vis detector, a fluorescence detector, a refractive index detector or an evaporative light scattering detector, in particular a vaporizing light scattering detector In this case, the response factor is constant, accurate composition analysis is possible without preparing a calibration curve by the reference material, and detection according to the gradient elution is possible, thus providing excellent effect of resolution and separation sensitivity.

In one embodiment of the present invention, a sample prepared at 1.0 mg / mL was injected into a loop volume of 100 μl using a Waters Vaporization Light Scattering Detector (ELSD) as the detector, and the transformation rate was measured.

A method for producing a rubber composition according to another embodiment of the present invention comprises polymerizing a conjugated diene monomer in the presence of a catalyst composition in a hydrocarbon solvent to prepare an active polymer; Modifying one end of the active polymer with a modifier having a purity of 92.0% or more to prepare a modified conjugated diene polymer; And the modified conjugated diene polymer; Filler; And a vulcanizing agent.

The relationship between the properties of the rubber composition, the modification ratio and the viscoelastic loss coefficient of the rubber composition, and the purity of the modifier are the same as those described above, and thus the description thereof will be omitted.

Also, in one embodiment of the present invention, the dynamic viscoelastic loss coefficient (tan delta) is used as an index of the fuel consumption characteristic, and the lower the dynamic viscoelastic loss coefficient value at 60 DEG C, the smaller the hysteresis loss, And thus shows excellent fuel economy.

In the present invention, the dynamic viscoelastic loss coefficient was measured at a frequency of 10 Hz and a strain of 3% at 60 ° C in a twist mode using a dynamic mechanical analyzer manufactured by TA, by vulcanizing the rubber composition at 150 ° C for 90 minutes.

In addition, the rubber composition according to an embodiment of the present invention contains the modified conjugated diene polymer in an amount of 0.1 wt% to 100 wt%, specifically 10 wt% to 100 wt%, more specifically 20 wt% to 90 wt% %. ≪ / RTI > If the content of the modified conjugated diene polymer is less than 0.1% by weight, the effect of improving the abrasion resistance and crack resistance of a molded article produced using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components, if necessary, in addition to the modified conjugated diene polymer, wherein the rubber component may be contained in an amount of 90 wt% or less based on the total weight of the rubber composition. Specifically, it may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene polymer.

The rubber component may be natural rubber or synthetic rubber, for example natural rubber (NR) comprising cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined with the general natural rubber; Butadiene copolymers (SBR), polybutadiene (BR), polyisoprenes (IR), butyl rubbers (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, neoprene, poly Butadiene), poly (styrene-co-butadiene), poly (styrene-co-butadiene) Synthetic rubber such as polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber and the like may be used, and any one or a mixture of two or more thereof may be used have.

In addition, the rubber composition may contain 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer, and the filler may be silica-based, carbon black or a combination thereof. Specifically, the filler may be carbon black.

The carbon black filler is not particularly limited, but may have a nitrogen adsorption specific surface area (measured according to N2SA, JIS K 6217-2: 2001) of 20 m 2 / g to 250 m 2 / g. The carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc / 100 g to 200 cc / 100 g. If the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² / g, the workability of the rubber composition may deteriorate. If it is less than 20 m ² / g, the reinforcing performance by carbon black may be insufficient. If the DBP oil absorption of the carbon black exceeds 200 cc / 100 g, the workability of the rubber composition may decrease. If the DBP oil absorption is less than 80 cc / 100 g, the reinforcing performance by carbon black may be insufficient.

The silica is not particularly limited, but may be, for example, wet silica (hydrated silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be a wet silica having the most remarkable effect of improving the breaking property and the wet grip. The silica has a nitrogen surface area per gram (N 2 SA) of 120 m 2 / g to 180 m 2 / g and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) of 100 m 2 / g to 200 m 2 / g Lt; / RTI > If the nitrogen adsorption specific surface area of the silica is less than 120 m < 2 > / g, the reinforcing performance by silica may be lowered. If it exceeds 180 m < 2 > / g, If the CTAB adsorption specific surface area of the silica is less than 100 m < 2 > / g, the reinforcing performance by the silica as a filler may be deteriorated. If it exceeds 200 m < 2 > / g, the workability of the rubber composition may deteriorate.

On the other hand, when silica is used as the filler, a silane coupling agent may be used together to improve the reinforcing property and the low heat build-up.

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzyltetrasulfide, 3-triethoxysilylpropylmethacrylate Monosulfide, monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl- N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. Any one or a mixture of two or more of them may be used. More specifically, in consideration of the reinforcing effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazine tetrasulfide.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur-crosslinkable including a vulcanizing agent, and the vulcanizing agent may be specifically sulfur powder, and may be used in an amount of 0.1 part by weight to 10 parts by weight ≪ / RTI > When contained in the above content range, the required elastic modulus and strength of the vulcanized rubber composition can be ensured, and at the same time, the low fuel consumption ratio can be obtained.

In addition, the rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, such as a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is not particularly limited and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil may be a paraffinic, naphthenic, or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, the process oil may be an aromatic process oil, a hysteresis loss And naphthenic or paraffinic process oils may be used in view of the low temperature characteristics. The process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. When the content is included in the above amount, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber can be prevented from lowering.

Specific examples of the antioxidant include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- 2, 4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone. The antioxidant may be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to one embodiment of the present invention can be obtained by kneading by using a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.

Accordingly, the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, Can be useful for the production of various industrial rubber products.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Production Example 1-1: Preparation of Catalyst Composition 1

A neodymium carboxylic acid compound was added to a hexane solvent under a nitrogen condition and diisobutylaluminum hydride (DIBAG) and diethylaluminum chloride (DEAC) were added to a neodymium compound: DIBAH: DEAC = 1: 9 to 10: , And then mixed to prepare a catalyst composition. The prepared catalyst composition was used immediately or after being stored under a nitrogen atmosphere at -30 to 20 ° C.

Production Example 1-2: Preparation of ethyl 1- (trimethylsilyl) piperidine-4-carboxylate

To a solution of 2 g of ethyl piperidine-3-carboxylate in dichloromethane (CH ₂ Cl ₂ ) was added at 0 ° C 1.77 ml of triethylamine (Et ₃ N) and trimethyl chloride adding a silyl (TMSCl ₃₎ 1.62 ml was added and stirred for 5 hours. Subsequently, the solvent in the resulting solution was evaporated under reduced pressure, redissolved in hexane and then filtered to obtain ethyl 1- (trimethylsilyl) piperidine-4-carboxylate, and analyzed by ¹ H nuclear magnetic resonance spectroscopy Respectively.

^{1 H NMR (500 MHz, CDCl} 3) δ 4.11-4.08 (m, 2H), 3.13-3.11 (m, 2H), 2.61-2.54 (m, 2H), 2.34-2.32 (m, 1H), 1.74 (m , 2H), 1.42 (m, 2H), 1.23-1.22 (m, 3H), 0.05-0.00 (m, 9H).

Production Example 2-1

Modified butadiene polymer having different modified ratios was prepared by controlling the modifier, the catalyst composition and the reaction conditions.

After vacuum and nitrogen were added alternately to the completely dried reactor, 4.7 kg (1,3-butadiene content = 500 g) of 1,3-butane diene / hexane mixed solution was put in a reactor in a vacuum state, After the prepared catalyst composition was added, polymerization reaction was carried out at 60 to 90 ° C for 15 to 60 minutes to prepare an active butadiene polymer containing an activated aluminum site at the terminal.

To this was added ethyl 1- (trimethylsilyl) piperidine-4-carboxylate prepared in Preparation Example 1-2 as a modifier and allowed to react for 30 to 60 minutes at the same temperature as the polymerization temperature ([denaturing agent] : [Nd] = 1 to 10: 1 equivalent). Thereafter, a hexane solution containing a polymerization terminator and a hexane solution containing an antioxidant were added to terminate the reaction.

The obtained polymer was put into hot water heated with steam and stirred to remove the solvent, followed by drying by roll to remove residual solvent and water to prepare a modified butadiene polymer.

Production example 2-2

Modified butadiene polymers were prepared in the same manner as in Preparation Example 2-1 except that the amounts shown in Table 1 were used as modifiers and the amounts shown in Table 1 (parts by weight relative to 100 parts by weight of the monomers) were used .

Comparative Production Examples 2-1 to 2-3

Modified butadiene polymers were prepared in the same manner as in Preparation Example 2-1 except that the amounts shown in Table 1 were used as modifiers and the amounts shown in Table 1 (parts by weight relative to 100 parts by weight of the monomers) were used .

Comparative Production Example 2-4

To the reactor which had been thoroughly dried, vacuum and nitrogen were alternately added. Then, 4.7 kg (1,3-butadiene content = 500 g) of 1,3-butane diene / hexane mixed solution was added to a reactor in a vacuum state, After the composition was added, the polymerization reaction was carried out at 70 DEG C for 60 minutes. Thereafter, a hexane solution containing a polymerization terminator and a hexane solution containing an antioxidant were added to terminate the reaction.

The obtained polymer was put into hot water heated with steam and stirred to remove the solvent, followed by drying by roll to remove the remaining solvent and water to prepare an unmodified butadiene polymer.

Evaluation of physical properties of polymer

The properties of the modified butadiene polymers prepared in Production Examples 2-1 to 2-5 were evaluated according to the following items, and the results are shown in Table 1 below.

1) Mooney viscosity (RP, raw polymer) and -S / R value

For each polymer, the Mooney viscosity (ML1 + 4, @ 100 ° C) (MU) was measured at 100 ° C under Rotor Speed 2 ± 0.02 rpm using Monsanto MV2000E with a large rotor. The sample used was allowed to stand at room temperature (23 ± 3 ° C) for more than 30 minutes, and then 27 ± 3 g was sampled and filled in the die cavity. Platen was operated to measure the Mooney viscosity by applying torque. Further, the Mooney viscosity was measured, and the change in Mooney viscosity as the torque was released was observed for 1 minute, and the -S / R value was determined from the slope value.

2) Measurement of sheath bond

The amount of cis bonds in each polymer was measured using Varian VNMRS 500 Mhz NMR, and 1,1,2,2-tetrachloroethane D2 (Cambridge Isotope) was used as a solvent.

3) Molecular weight distribution (MWD)

Each of the polymers was dissolved in tetrahydrofuran (THF) for 30 minutes under the condition of 40 占 폚 and loaded on gel permeation chromatography (GPC). At this time, two columns of PLgel Olexis column and one column of PLgel mixed-C column of Polymer Laboratories were used in combination. In addition, a column of a mixed bed type was used as a new column, and polystyrene was used as a gel permeation chromatography (GPC) standard material.

4) Purity measurement of denaturant

The purity of the denaturant was measured by using a gas chromatograph and a mass spectrometer (Mass Seproscopy). The purity of the denaturant was measured through the% peak area of the target material.

5) Measurement of metamorphic rate

The polymer was dissolved in cyclohexane, stored in mobile phase reservoirs (each with 1.0 mg / ml) and tetrahydrofuran (THF) in another mobile phase. The mobile phase reservoir was connected to a dual-head pump, respectively, and a solution of the polymer-dissolved mobile phase reservoir was first injected through a pump and an injector with a loop volume of 100 μl into a column filled with silica adsorbent. At this time, the pressure of the pump was 450 psi and the flow rate of the injection was 0.7 ml / min. The tetrahydrofuran was then injected into the column via a pump, based on the 5 minutes from the start of the injection, confirming that the unmodified butadiene polymer units in the polymer were no longer detected from the detector (ELSD, Waters). At this time, the pressure of the pump was 380 psi and the flow rate of the injection was 0.7 ml / min. Upon injection of the tetrahydrofuran from the detector, it was confirmed that the denatured butadiene polymer units in the polymer were no longer detected and the injection of the second solvent was terminated. Subsequently, the percent modification (%) was calculated from the detected chromatogram results according to the following equation (2).

&Quot; (2) "

division	Production Example 2-1	Production example 2-2	Production Example 2-3	Comparative Production Example 2-1	Comparative Production Example 2-2	Comparative Production Example 2-3	Comparative Production Example 2-4
Denaturant input	0.23	0.23	0.23	0.25	0.24	0.23	-
Denaturant purity	93.4	92.2	90.5	89.0	89.0	89.0	-
Calculated input *	0.215	0.212	0.208	0.225	0.214	0.205	-
Metamorphic rate	41	29	26	22	20	18	0
Mooney viscosity	43.7	46.0	44.3	45.2	44.3	42.3	47.3
-S / R	0.694	0.582	0.602	0.593	0.588	0.507	0.647
Cis bond content (cis)	97.9	96.7	96.8	96.8	96.8	96.3	96.9
Molecular Weight Distribution (MWD)	2.69	2.60	2.61	2.64	2.64	2.64	2.53

* Calculated input: Purity calculated on the input of the denaturant

Referring to Table 1, it can be seen that the higher the purity of the modifier, the higher the modifying rate and thus the linearity and the cis-bond content are gradually improved. In addition, it can be seen that the beta value is remarkably high as compared with the unmodified comparative production example, and as a result, a polymer having excellent linearity can be produced.

Further, in Production Examples 2-1 and 2-2 and Comparative Production Examples 2-2 to 2-4, when the amounts are substantially the same and the actual amounts of the modifier calculated by the purity of the modifier are larger (Comparative Examples 1 and 2) It can be seen that the purity of the denaturant affects the denaturation rate in consideration of the fact that the denaturation rate differs according to the purity. In addition, in Examples 2-1 to 2-3 and Comparative Example Comparing with 2-3, it can be confirmed that the purity is increased to about 90%, and the purity is greatly increased, and it can be confirmed that the purity is increased again by 93%. That is, when the purity of the modifier is 90% or more, it can be confirmed that an excellent modification ratio can be obtained.

Examples 1 to 3, Comparative Examples 1 to 3

70 parts by weight of carbon black, 22.5 parts by weight of a process oil, 10 parts by weight of a process oil, and 100 parts by weight of a modified butadiene polymer prepared in Preparation Examples 2-1 and 2-2 and Comparative Preparative Examples 2-1 to 2-3, 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid were mixed to prepare a first composition. Subsequently, 2 parts by weight of sulfur, 2 parts by weight of a vulcanization accelerator (CZ) and 0.5 parts by weight of a vulcanization accelerator (DPG) were added to each of the above primary compositions and mixed at 50 rpm for 1.5 minutes at 50 rpm.

The dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C was predicted according to the following formula (1).

[Equation 1]

In the above formula (1), X is the modifying ratio of the modified conjugated diene polymer, and A is the dynamic viscoelastic loss coefficient (tan delta) of the rubber composition containing the unmodified conjugated diene polymer at 60 DEG C, 0.152, and Y is the dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of the rubber composition containing the modified conjugated diene polymer.

division	Purity of the denaturant	X (metamorphic rate)	Y (Viscoelastic loss coefficient)	A
Example 1	93.4	41	0.1245	0.1520
Example 2	92.2	29	0.1335
Example 3	90.5	26	0.1359
Comparative Example 1	89.0	22	0.1394
Comparative Example 2	89.0	20	0.1411
Comparative Example 3	89.0	18	0.1430

Comparative Example 4

A rubber composition was prepared in the same manner as in Example 1, except that the unmodified butadiene polymer prepared in Comparative Preparation Example 2-4 was used in place of the modified butadiene polymer.

Experimental Example

Specimens were prepared using the rubber compositions prepared in the above Examples and Comparative Examples, and tensile properties and viscoelastic characteristics were measured and are shown in Table 3 below.

Each specimen was prepared by vulcanizing each rubber composition at 160 DEG C for 25 minutes.

1) Evaluation of tensile properties

The tensile properties of the prepared specimens were measured by measuring the tensile stress at 300% elongation (300% modulus) when the test specimen was cut at 150 DEG C for 90 minutes and according to the tensile test method of ASTM D412. At this time, each measured value was indexed by setting the measured value of the comparative example at 100.

2) Evaluation of viscoelastic properties

The viscoelastic properties of the prepared specimens were measured using a dynamic mechanical analyzer from TA Corporation at a frequency of 10 Hz and a strain rate of 3% at 60 DEG C in a torsional mode. At this time, Index was indexed by setting the measured value of the unmodified polymer to 100. On the other hand, the tan? Value at 60 占 폚 shows the fuel efficiency.

division	Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2	Comparative Example 3	Comparative Example 4
300% modulus (kgf / cm 2 )	113	109	110	107	106	110	107
Tanδat 60 ℃	0.124	0.131	0.133	0.139	0.141	0.145	0.152
Tin 60 ° C (Index)	122	116	114	109	108	105	100

As shown in Table 3, Tan δ at 60 ° C. of each of the rubber compositions of Examples 1 to 3 exhibited a value substantially similar to each Y value described in Table 1, and had a value of 0.14 or less, It is confirmed that the characteristics are excellent.

This indicates that the accuracy of the formula (1), which is a regression equation showing the correlation between the modifying ratio of the modified conjugated diene polymer according to the present invention and the dynamic viscoelastic loss coefficient at 60 캜 of the rubber composition, is high, It can be confirmed that the rubber composition having the following excellent viscoelastic coefficient can be provided even without measuring it.

In order to produce a rubber composition having excellent viscoelastic properties through the above-mentioned results, the modification ratio is determined by using Equation 1, and this modification ratio can be controlled through the purity of the modifier, As shown in Fig.

Claims (13)

1. A modified conjugated diene polymer; Filler; And a vulcanizing agent,

   Satisfies the following expression (1)

   Wherein the modified conjugated diene polymer is modified with a modifier having a purity of not less than 90.0%

   [Equation 1]

   

   In the above formula (1), X is the modifying rate of the modified conjugated diene polymer,

   A is a dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of a rubber composition containing an unmodified conjugated diene polymer and has a real value of 0.140 to 0.160,

   Y is the dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of the rubber composition containing the modified conjugated diene polymer.
2. The method according to claim 1,

   Wherein the modified conjugated diene polymer is a lanthanide-based rare earth element-containing catalyzed conjugated diene polymer containing at least one functional group.
3. The method according to claim 1,

   Wherein the modifier has a purity of 93.0% or more.
4. The method according to claim 1,

   Wherein the modified conjugated diene polymer is a lanthanide-based rare earth element-containing catalyzed conjugated diene polymer containing at least one functional group.
5. The method according to claim 1,

   The rubber composition comprises 100 parts by weight of a modified conjugated diene polymer; 0.1 to 150 parts by weight of a filler; And 0.1 to 10 parts by weight of a vulcanizing agent.
6. The method according to claim 1,

   The modification ratio is a value calculated according to the following formula (2) using a chromatogram obtained from a chromatographic measurement,

   The chromatographic measurement can be carried out,

   Preparing a first solution by dissolving a polymer comprising a modified polymer unit and an unmodified polymer unit in a first solvent;

   Injecting the first solution into a column filled with adsorbent;

   Adsorbing the modified polymer unit to the adsorbent, and eluting the first solution in which the unmodified polymer unit is dissolved;

   Transferring the eluted first solution to a detector;

   Introducing a second solvent into the column to elute the second solution in which the adsorbed modified polymer units are dissolved; And

   And transferring the eluted second solution to the detector.

   &Quot; (2) "

   

   In Equation (2)

   The peak area of the unmodified polymer is the peak area of the chromatogram for the first solution transferred to the detector and the peak area of the modified polymer is the peak area of the chromatogram for the second solution transferred to the detector.
7. The method of claim 6,

   Wherein the adsorbent is a silica-based adsorbent.
8. The method of claim 6,

   Wherein the first solvent and the second solvent are each independently a polar solvent or a non-polar solvent, and the first solvent and the second solvent have opposite polarities.
9. The method of claim 8,

   The polar solvent may be selected from the group consisting of water, methanol, ethanol, n-propanol, n-butanol, isopropanol, formic acid, acetic acid, acetone, nitromethane, propylene carbonate, The organic solvent is selected from the group consisting of dioxane, tetrahydrofuran (THF), acetonitrile (MeCN), dimethylformamide (DMF), dimethylsulfoxide (DMSO), methyl ethyl ketone, benzonitrile, pyridine, nitroethane, wherein the rubber composition is at least one selected from the group consisting of benzyl alchol, methoxy ethanol and formamide.
10. The method of claim 8,

    The nonpolar solvent is selected from the group consisting of hexane, benzene, toluene, diethyl ether, chloroform, ethyl acetate, dichloromethane, cyclohexane, tetrachloromethane, iso-octane, xylene, butyl ether, , Isopropyl ether, and ethylene chloride.
11. A modified conjugated diene polymer; Filler; And a vulcanizing agent,

    Satisfies the following expression (1)

    The modified conjugated diene polymer is modified with a modifier having a purity of not less than 90.0%

    Wherein the modifier is represented by the following formula (1) or (2):

    [Equation 1]

    

    In the above formula (1), X is the modifying rate of the modified conjugated diene polymer,

    A is a dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of a rubber composition containing an unmodified conjugated diene polymer and has a real value of 0.140 to 0.160,

    Y is the dynamic viscoelastic loss coefficient (tan delta) of the rubber composition containing the modified conjugated diene polymer at 60 DEG C,

    [Chemical Formula 1]

    

    (2)

    

    In the above formula (1) or (2)

    Z ₁ and Z ₂ are each independently a silane group, an N, N-2-substituted amino-phenyl group, an imine group or a cyclic amino group,

    R ₁ and R ₇ are, independently of each other, a single bond or a divalent organic group,

    R ₃ and R ₆ are, independently of each other, a single bond or a divalent organic group; Are each a trivalent organic group connected to R ₄ or R ₅ and R ₈ or R ₉ to form a ring,

    R ₄ and R ₈ are each independently a monovalent organic group; Or a divalent organic group which is linked to R ₃ or R ₅ and R ₆ or R ₉ , respectively, to form a ring,

    R ₅ is a monovalent organic group; Or R < ₃ > or R < ₄ > to form a ring.
12. Polymerizing a conjugated diene monomer in the presence of a catalyst composition in a hydrocarbon solvent to produce an active polymer;

    Modifying one end of the active polymer with a modifier having a purity of 90.0% or more to prepare a modified conjugated diene polymer; And

    The modified conjugated diene polymer; Filler; And a vulcanizing agent.
13. The method of claim 12,

    Wherein the rubber composition satisfies the following formula (1): " (1) "

    [Equation 1]

    

    In the above formula (1), X is the modifying rate of the modified conjugated diene polymer,

    A is a dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of a rubber composition containing an unmodified conjugated diene polymer and has a real value of 0.147 to 0.160,

    Y is the dynamic viscoelastic loss coefficient (tan delta) at 60 DEG C of the rubber composition containing the modified conjugated diene polymer.

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